Lubricant and fuel compositions

ABSTRACT

HIGH MOLECULAR WEIGHT N-HYDROCARBYL-SUBSTITUTED QUATERNARY AMMONIUM SALTS IN WHICH THE HYDROCARBYL GROUP HAS A MOLECULAR WEIGHT OF FROM ABOUT 350-3000 SUCH AS A POLYBUTENE AMMONIUM CHLORIDE ARE EFFECTIVE DETERGENTS AND DISPERSANTS FOR GASOLINE AND LUBRICATING OILS.

United States Patent Oflice 3,778,371 Patented Dec. 11, 1973 3,778,371LUBRICANT AND FUEL COMPOSITIONS Robert E. Malec, Birmingham, Mich.,assignor to Ethyl Corporation, Richmond, Va. No Drawing.Continuation-impart of abandoned application Ser. No. 138,758, Apr. 29,1971. This application May 19, 1972, Ser. No. 255,223 Int. Cl. Cm 1/32;C101 1/22 U.S. Cl. 252-34 33 Claims ABSTRACT OF THE DISCLOSURE Highmolecular weight N-hydrocarbyl-substituted quaternary ammonium salts inwhich the hydrocarbyl group has a molecular weight of from about350-3000 such as a polybutene ammonium chloride are efiective detergentsand dispersants for gasoline and lubricating oils.

PRIOR APPLICATIONS This application is a continuation-in-part ofapplication Ser. No. 138,758, filed Apr. 29, 1971, now abandoned.

BACKGROUND High molecular weight hydrocarbyl amines such as polybuteneamines and polyamines are known as detergents and dispersants in fuelsand lubricants (Wagenaar, U.S. 3,275,554; Honnen et al., U.S. 3,438,757;Honnen et al., U.S. 3,565,804). These compounds are prepared by reactingan appropriate hydrocarbyl halide with a primary or secondary amine orpolyamine under conditions such that hydrogen halide .is eliminated Lowmolecular weight quaternary ammonium thiocarbamates and thiophosphates,such as dioleyl dimethylammonium dithiocarbamate or alkylbenzyl dimethylhydroxyethylammonium 0,0 dialkylphosphorodithioate, have been evaluatedas antioxidants in lubricating oils (B. W. Hotten, Preprints, ACSDivision of Petroleum Chemistry, vol. 13, No. 2, pages B-67-71, April1968). Low molecular weight hydrocarbyl ammonium hydroxides, such asdioleyl dimethylammonium hydroxide, a strong base, have been used ingasoline as carburetor detergents (Barusch et al., U.S. 3,468,640).

SUMMARY OF THE INVENTION The present invention relates to new highmolecular weight quaternary ammonium salts having an aliphatichydrocarbon group with a molecular weight of from about 350-3000 bondedto a quaternary ammonium nitrogen atom. The anion of the salt may be anyof'the well-known salt anions, such as halides (chloride, bromide,fluoride, iodide), nitrite, nitrate, carbonate, borate, alkylborates,bicarbonate, alkanoate (e.g., acetate), phosphate, alkylphosphates,dialkylphosphates, dialkyldithiophosphates, and the like. The newcompounds are useful as ashless dispersants in lubricating oils and ascarburetor detergents in gasoline.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of thisinvention is a high molecular weight quaternary ammonium salt having atleast one aliphatic hydrocarbon group having an average molecular weightof from about 350-3000 bonded to a quaternary ammonium nitrogen atom.

These compounds can be represented by the formula:

V [RpN-Ra] Z l.

in which as least one of R R R and R is an aliphatic hydrocarbon grouphaving a molecular weight of about 350-3000 and the remaining R groupsare independently selected from C alkyl, C hydroxyalkyl, C alkenyl, orare joined to form a morpholine, piperidine or pyridine ring, and Z is asalt anion. Preferably, the high molecular weight hydrocarbon group issubstantially saturated, although minor amounts up to about 5 percentare acceptable. It is also preferred that only one of R R R and R is ahigh molecular weight substantially saturated aliphatic hydrocarbongroup.

The quaternary ammonium salt may be the quaternary ammonium salt of apolyamine wherein the nitrogen atom in Formula I represents but onequaternary ammonium nitrogen atom in said polyamine and is joinedthrough one of the R groups to one or more other quaternary ammoniumnitrogen atoms. In this case the bridging group represented by one ormore of the R groups is a divalent hydrocarbon group containing from 2to about 4 carbon atoms, such as an ethylene (CH -CH group. An exampleis the high molecular weight aliphatic hydrocarbyl quaternary ammoniumsalt of N,N,N',N'- tetraalkyl ethylene diamine such asN,N,N',N'-tetraethyl ethylene diamine. Likewise, two of the R groups mayform a bridge to a single quaternary ammonium nitrogen atom such aswould be derived by quaternizing an N,N'-dialkyl piperazine.

In an especially preferred embodiment, three of the R group are ethylenegroups and form a bridge to a second nitrogen atom. These compounds arequaternary ammonium salts of the compound triethylenediamine, a cagestructure compound having the formula:

Since this compound has two tertiary nitrogen atoms it is possible tomake both monoand di-high molecular weight aliphatic hydrocarbonquaternary ammonium salts having the following formula:

wherein R is a substantially saturated aliphatic hydrocarbon grouphaving an average molecular weight of from 350-3000, more preferablyfrom about 800-1400, and n is l or 2. The practice, the salts aregenerally mixtures of both monoand di-aliphatic hydrocarbon quaternaryammonium "salts such as monoand di-polybutene quaternary ammoniumchlorides, phosphates, alkylphosphates, dialkylphosphates, borates,alkyl borates, nitrites, and the like. The preferred salts arechlorides.

The quaternary ammonium salts can be made by known methods such asreacting a high molecular weight aliphatic hydrocarbon halide in whichthe hydrocarbon group has a molecular weight of from about 350-3000 withan appropriate tertiary amine at -200 C., as depicted in the followingequation:

In this reaction, R is a high molecular weight (350- 3000) aliphatichydrocarbon, and R R and R are the same as in Formula I and Z is achloride, bromide, iodide or fluoride anion as represented by Z inFormula I. Solvents such as aliphatic hydrocarbons boiling from 50-200C. can be used as well as aromatic hydrocarbons such as benzene,toluene, xylene, and the like. The reaction results in the formation ofa high molecular weight hydrocarbyl-substituted quaternary ammoniumhalide. The halide anion can be readily replaced by another anion byknown methods such as adding a large stoichiometric excess of a saltcotaining the desired replacement anion to the quaternary ammoniumchloride and stirring at 50200 C. to displace the chloride anion. Themixture can then be filtered and water washed.

Also, as described above, the tertiary amine used in preparing thequaternary ammonium salt may be a polyamine containing tertiary aminegroups. Some representative examples of amine reactants which can bequaternized to yield compounds of this invention are:

trimethyl amine triethyl amine tri-n-propyl amine dimethylethyl aminedimethyl lauryl amine dimethyl oleyl amine dimethyl stearyl aminedimethyl eicosyl amine dimethyl octadecyl amine N-methyl piperidineN,N'-dimethyl piperazine N-methyl-N'-ethyl piperazine N-methylmorpholine N-ethyl morpholine N-hydroxyethyl morpholine pyridinetriethanol amine triisopropanol amine methyl diethanol amine dimethylethanol amine lauryl diisopropanol amine stearyl diethanol amine dioleylethanol amine dimethyl isobutanol amine methyl diisooctanol aminedimethyl propenyl amine dimethyl butenyl amine dimethyl octenyl amineethyl didodecenyl amine dibutyl eicosenyl amine triethylene diaminehexamethylene tetramine N,N,N',N'-tetramethylethylenediamineN,N,N',N'-tetraethyl-l,3-propanediamine methyldicyclohexyl aminelutidine From the above, it is apparent that the particular amine is notcritical. The critical feature of the invention is the long aliphatichydrocarbon group having an average molecular weight of from about350-3000 and having a quaternary ammonium salt group at one end. Anyquaternary ammonium salt group will perform, although not all to thesame degree of effectiveness, as long as the high molecular weightaliphatic hydrocarbyl group is attached to the quaternary ammoniumnitrogen atom. Such high molecular weight aliphatic hydrocarbyl groupscontaining from about to over 200 carbon atoms.

The aliphatic hydrocarbon group can be any such group that has therequired molecular weight. For example, the group may be ob ain d frommineral oil sources such as the thermal cracking of parafiin wax. Thepreferred hydrocarbon groups are those derived from polymonoolefins,such as polyethylenes, polypropylenes, polybutenes, polyhexenes,polyoctenes, polydecenes, polydodecenes, and the like. Preferably, theolefin monomers are l-olefins. The polylefins made from C olefinmonomers are preferred such as polypropylene and polybutene. Of these,polybutene, such as polyisobutylene, is especially preferred because ofthe good performance of the products obtained and the commercialavailability of the polybutenes. The quaternary salts prepared frompolyolefin halides such as polybutene chloride are referred to aspolyolefin quaternary ammonium salts, e.g., polybutene pyn'diumchloride, polybutene tri-lower alkyl ammonium chloride, or monoordi-polybutene quaternary ammonium chloride of triethylene diamine.

The molecular Weight of the aliphatic hydrocarbon group is veryimportant. The lower aliphatic hydrocarbon groups do not impart the allaround effectiveness, espe cially as ashless lubricating oildispersants, that results when a high molecular weight aliphatichydrocarbon group is bonded to the quaternary ammonium nitrogen atom. Apreferred molecular weight range is from about 350-3000. Superiorresults are obtained when the hydrocarbon group has a molecular weightof from about 800l400.

As mentioned earlier, the salt anion can be any of the common saltanions, such as chloride, bromide, fluoride, iodide, nitrite, nitrate,borate, alkylborate, carbonate, bicarbonate, alkanoate (e.g., acetate,propionate, butyrate, and the like), phosphate, alkylphosphate,dialkylphosphate, 0,0-dialkyldithiophosphate, and the like. Thepreferred anions are halides. Of these, bromide and chloride areespecially preferred. The most preferred anion is chloride.

Representative examples of quaternary ammonium salts of this inventioninclude:

polybutene (M.W. 3000) trimethylammonium chloride polybutene (M.W. 1000)triethylamrnonium iodide polybutene (M.W. 350) tri-n-propylammoniumbromide polypropylene (M.W. 1500) pyridinum dioctylphosphate C Htri-n-butylammonium nitrite polybutene (M.W. 1000) triethanolammoniumethyl borate polypropylene chloride polypropylene (M.W. 900)tri-methylammonium 0,0-dieicosyl dithiophosphate dipolybutene (M.W. 900)triethylenediammonium dichloride dipolypropylene (M.W. 1100)triethylenediammonium dichloride Further examples will be apparent toany chemist by mere inspection of the previous list of tertiary amineswhich may be quaternized by a high molecular weight substantiallysaturated aliphatic hydrocarbon halide to produce the initial quaternaryammonium halide which may, if desired, be converted to various suchsalts by exchanging anions by known methods.

The quaternary ammonium dispersants and detergents of this invention aremore easily made compared to the methods required to prepare similarprior art additives. For example, the preparation of the hydrocarbylamine detergents requires the reaction of an appropriate hydrocarbylhalide with a primary or secondary amine for long periods of time atelevated temperatures. The conditions must be such that the hydrogenhalide is eliminated according to the reaction:

The hydrogen halide formed must be removed or the product could causecorrosion. No such restrictions are placed on the preparation of thepresent additives. The high molecular weight hydrocarbyl halide ismerely (M W. 800) N-ethanolmorpholinium mixed with the appropriatetertiary amine and warmed to form the quaternary ammonium salt. Hydrogenhalide is not expelled from the reaction.

The high molecular weight aliphatic hydrocarbyl halides used toquaternize the amine can be made by known methods, such as thewell-known halogenation of aliphatic hydrocarbons. The high molecularweight aliphatic hydrocarbon can be obtained from any source, such asthe thermal cracking of parafiin wax or, preferably, from thepolymerization of olefins. The polyolefin starting material ispreferred. The olefins used to prepare the starting material can be anyolefin hydrocarbon, such as those containing from 2 to about 32 carbonatoms. The higher olefins such as those containing from 12-32 carbonatoms need not be polymerized to a great extent, but need only bedimerized, trimerized or tetramerized to obtain the required molecularweight. Such olefin polymers are described more fully later, since theycan also be used together with compounds of this invention as gasolineadditives. Thus, in one embodiment of the invention the polyolefinstarting material is a mixture of oligomerized C1242 olefins in whichthe oligomer has a molecular weight of from about 350-4500.

The preferred polyolefin starting material is the poly- C olefins,especially the poly-C olefins. Any of the polyolefins are readilyhalogenated by merely passing a halogen into the material at moderatetemperatures.

This halogenation can be carried out under relatively mild conditions.The temperature at which the reaction can be carried out may be variedover a wide range. Thus, the halogenation can be accomplished attemperatures ranging from 50 to 150 C. In general, the halogenation iselfected by dissolving the polyolefin in a solvent such as benzene,tetrahydrofuran, and the like, and treating the solution with thehalogen, for example, chlorine gas, or a halogenating reagent, such asN-bromo succinimide. The polyolefin halide is also obtained byhalogenating polyolefin without any solvent being present. The physicalcharacteristics of the polyolefin, for example, its viscosity, will helpdetermine whether a solvent should be used. The halogenation proceedswhether a solvent is used or not. The reaction is generally complete in15 to 120 minutes. The following examples will illustrate typicalhalogenation procedures. All parts are by weight unless otherwisespecified.

EXAMPLE 1 A solution of 301 parts of Polybutene-24 (Chevron ChemicalCompany designation for polyisobutylene of molecular weight about 950)in 120 parts of benzene was placed in a vessel equipped withthermometer, stirrer, gas inlet tube and condenser. The solution washeated to about 73 C. and 22.7 parts of chlorine gas was bubbled throughover a period of about one hour.

The reaction vessel was then flushed with nitrogen gas for one hour. Thesolution was filtered and the solvent was removed by vacuumdistillation. The yield was 312 parts of polyisobutyl chloride. Theproduct was a cloudy orange-colored viscous liquid, which on analysiswas found to contain 3.55 percent chlorine. Infrared analysis showedthat the compound was unsaturated.

EXAMPLE 2 A reaction vessel fitted with a thermometer, stirrer andcondenser was charged with 94.1 parts of Polybutene-24 (defined inExample 1), 17.8 parts of N-bromo succinimide and 200 parts of benzene.This mixture was re- :tluxed for about 30 minutes. The mixtures was thencooled and the solution was filtered. The solvent was stripped and theresidue was then redissolved in hexane. This solution was filtered andthe solvent was removed by vacuum distillation. A 99 percent yield ofthe polyisobutyl bromide was obtained as a dark brown viscous liquid.The bromine content of this product was 7.9 percent.

6 The following example illustrates the halogenation of a polyolefinfollowed by quaternization of the resultant hydrocarbyl halide.

EXAMPLE 3 In a reaction vessel was placed 180 parts of polybutene(average molecular weight 800) and parts of henzene. Chlorine was passedinto the solution at 80-90 C. for one hour. The system was then purgedof chlorine by passing nitrogen through it for an hour. Following this,40 parts of pyridine was added and the mixture stirred at -130 C. for 3hours. The resultant product was washed with water and then heated undervacuum to remove solvent. It was diluted with an SAE-lO neutral mineraloil to form a 50 weight percent active concentrate of polybutenepyridinium chloride in which the polybutene group bonded to thequaternized pyridinium nitrogen atom had an average molecular weight of800. Polybutene and polybutenyl as well as polypropylene andpolypropenyl when referring to aliphatic hydrocarbon groups are usedinterchangeably herein.

The following examples illustrate the replacement of the chloride anionwith various other anions.

EXAMPLE 4 In a reaction vessel was placed 25 parts of the polybutenepyridinium chloride from Example 3 and 13 parts of O,O-di-C alkyl zincphosphorodithioate. To this mixture was added about 25 parts ofpetroleum ether and the mixture was stirred at reflux for 30 minutes.The mixture was cooled and filtered to remove the zinc chlorideprecipitate and the filtrate washed with water. It was then heated undervacuum to distill out the petroleum ether. The product was anoil-diluted concentrate containing polybutene pyridinium O,O-di-C alkylphosphorodithioate.

EXAMPLE 5 In a reaction vessel was placed 25 parts of the polybutenepyridinium chloride from Example 3, 25 parts of petroleum ether and 5parts of sodium nitrite dissolved in a water-methanol mixture. Themixture was heated and stirred for 30 minutes. The small aqueous phasepresent was then removed and the product heated under vacuum to distillout solvent. The remaining product was filtered, yielding a mixturecontaining polybutene pyridinium nitrite.

EXAMPLE 6 In a reaction vessel was placed 25 parts of the polybutenepyridinium chloride from Example 3 and 6.25 parts of sodium dibutyldithiocarbamate. Twenty parts of petroleum ether were added and themixture stirred at reflux for 30 minutes. The product was filtered andthe solvent distilled off under vacuum, resulting in a concentratecontaining polybutene pyridinium dibutyl dithiocarbamate.

EXAMPLE 7 In a vessel was placed 25 parts of the polybutene pyridiniumchloride from Example 3 and 5 parts of tridecyl hydrogen phosphate. Themixture was stirred and heated under vacuum for one hour, during whichperiod hydrogen chloride evolved. The resultant mixture was an oilconcentrate containing polybutene pyridinium tridecylphosphate.

EXAMPLE 8 In a closed reaction vessel place 1000 parts of polypropylenebromide (made by brominating polypropylene having an average molecularweight of 950). Add 500 parts of toluene and 90 parts of trimethylamine. Stir and heat the mixture to reflux. Reflux for an hour and thencool and wash twice with 500 part portions of water. Heat to about C.under vacuum (approximately 10 mm. Hg) to distill out the toluenesolvent. The product is a polypropenyl trimethyl ammonium bromide inwhich the 7 polypropenyl group has an average molecular weight of 950.

Other amines can be used in the above example with good results. Thefollowing table lists such other amines and the corresponding productwhich forms.

Amine Quaternary ammonium salt 'lriethyl amine Polygropenyl triethylammonium bromi e.

Lauryl dimethyl amine Polypropenyl lauryl dimethyl ammonium bromide.

Eicosyl dimethyl amine Polypropenyl eicosyl dimethyl ammonium bromide.

Dioleyl methyl amine Polypropenyl dioleyl methyl ammonium bromide.

Distearyl ethyl amine Prglyprogenyl distearyl ethyl ammonium romi e.

Dilauryl methyl amine Polypropenyl dilauryl methyl ammobromide.

N-methyl piperidino Polygropenyl methyl pyridininm broml e.

N-methyl morpholine Polypropenyl methyl morpholinium bromide.

Triethanol amine Polypropenyl tri(2-hydroxyethyl)ammonium bromide.

Dlethanol ethyl amine Polypropenyl di(2-hydroxyethyl) ethyl ammoniumbromi e.

N,N,N, -tetramethyl eth- Dipolypropenyl tetramethyl ethylene ylenediamine. diammonlum bromide.

Nitrilotriacetonitrile Polypropenyl triaeeto nitrile ammomum bromide.

EXAMPLE 9 In this example the starting hydrocarbon is an olefin oligomerprepared by polymerizing a mixture of C 1- olefins using an aluminumchloride catalyst to obtain an oligomer having an average molecularweight of 550. The preparation of this oligomer will be described later.

In a reaction vessel place 550 parts of the above oligomer and heat to80-90 C. Pass chlorine into the liquid until one mole part has reacted.Following this, pass nitrogen through the liquid for 10 minutes toremove residual chlorine. Then add 100 parts of pyridine and 250 partsof toluene. Heat the mixture to 130 C. and stir for an hour. Cool andwash with water and then distill out the toluene under vacuum. Add 630parts of an SAE-lO neutral mineral oil to obtain a 50 weight percentactive concentrate of a poly-C l-olefin pyridininm chloride.

Other hydrocarbons having an average molecular weight of from about350-3000 can be used in the above example in place of the poly-Cl-olefin. These can be obtained directly from mineral oil or can bethermally cracked parafiin wax. Likewise, polymers of lower l-olefinssuch as polypropylene or polyisobutylene can be used with excellentresults.

EXAMPLE 10 In a reaction vessel wa placed 200 grams of polybutenechloride (from polybutene having an average molecular weight of 950) and30 grams of dimethyl acetamide. The mixture was heated to 90 C. andtrimethylamine was bubbled through it for 1.75 hours. The resultantproduct was distilled under vacuum to remove volatiles and the residualliquid diluted with 100 grams of light mineral oil, giving a detergentconcentrate of polybutene trimethyl ammonium chloride.

EXAMPLE 1 1 In a reaction vessel was placed 20 grams of the polybutenetrimethylammonium chloride from Example 10 and 2 grams of hexyleneglycolacid borate. The mixture was stirred and heated on a steam bath for onehour and then distilled under vacuum, yielding a polybutenetrimethylammonium hexyleneglycol borate.

EXAMPLE 12 In a reaction vessel as used in Example 1 was placed 200grams of polybutene chloride prepared as in Example 1. To this was added13.4 grams of triethylenediamine and 40 grams of methylethyl ketonesolvent. The mixture was stirred at l30137 C. for one hour and thendiluted with 75 grams of light mineral oil and 30 grams of ndodecanol.The concentrate was diluted with an equal volume of hexane and washedfirst with lime water and then with water. It was then filtered and thevolatiles distilled out under vacuum, yielding 303 parts of a dispersantconcentrate (approximately 67 percent active).

EXAMPLE 13 In a reaction vessel as used in Example 1 was placed 50 gramsof polybutene chloride (from Example 1), 7 parts ofhexamethylenetetramine and 15 parts of N,N- dimethyl acetamide solvent.The mixture was stirred for minutes at ISO-155 C. to form a polybutenylquaternary ammonium chloride of hexamethylenetetramine.

EXAMPLE 14 In a reaction vessel was placed 100 grams of polybutenechloride (from Example 1) and 200 grams of pyridine. The mixture wasstirred at 188 C. for 3.5 hours, following which unreacted pyridine wasdistilled out at reduced pressure. The product was diluted with an equalvolume of hexane and filtered. The hexane was distilled out and theproduct diluted with 54 grams of light mineral oil to give 163 grams of67 percent active polybutenyl pyridininm chloride.

The alkyl hydrogen phosphate salt was prepared by heating a mixture ofn-decanol and dodecanol and P 0 for 2 hours at -95 C. It was dilutedwith petroleum ether and water washed. It was converted to its sodiumsalt by adding 53 grams of sodium hydroxide to bring the pH to 8-9.

The above polybutenyl pyridininm chloride was converted to an alkylphosphate salt by mixing 50 grams of the chloride salt with 5 grams ofthe above sodium alkyl phosphate, diluting the mixture with hexane andstirring for 6 hours at reflux. The product was washed with' water toremove sodium chloride and the hexane distilled out under vacuum toleave a polybutenyl pyridinium alkyl phosphate.

EXAMPLE 15 In a reaction vessel was placed 634 grams of polybutenechloride (average molecular weight 950) and 500 ml. of chlorobenzene.The mixture was heated to 130 C. and chlorine injected for one hour and35 minutes. Solvent was distilled out, leaving a polybutene chloride.

In a second reaction vessel was placed grams of the above polybutenechloride, 6.7 grams of triethylenediamine and 50 grams of methylethylketone. The mixture was stirred one hour at 9093 C., diluted withhexane, water washed and filtered. It was then diluted with 50 grams oflight mineral oil and distilled under vacuum to remove volatilematerials.

EXAMPLE 16 One-half of the product prepared in Example 15 was added to asaturated solution of sodium nitrite in dimethylformamide. The mixturewas heated to reflux and stirred 30 minutes following which it waswashed with water and distilled to remove voatiles, resulting in aresidue containing polybutenyl quaternary ammonium nitrate salt oftriethylenediamine.

The quaternary ammonium salts of this invention are excellentdispersants for lubricating oil including both synthetic (e.g., esterbased oils) and mineral lubricating oils. Tests were carried out todemonstrate their effectiveness.

SLUDGE DISPERSANCY TEST In this test a test blend is prepared using 7grams of a typical engine sludge material, 2 grams of water, one gram oftest additive and suflicient neutral mineral oil to make a 100-gramblend. This material is emulsified in a blender for 20 minutes and thencentrifuged for 2.5 hours. Following this, the percent lighttransmittance of the oil just beneath the surface is measuredphotoelectrically. The better the disperant, the more of the PercentCone. (wt. light transpercent) mittance None 59 Additive of Example:

As the above tests show, the dispersants 0f the present inventionretained the sludge in a dispersed form even after 2.5 hours ofcentrifuging to such a degree that as little as 1 percent of the lightwould transmit through the oil compared to 59 percent of the light whichwas transmitted through the non-dispersant oil.

Additives of this invention have been subjectedto engine tests. Thetests employed were standard L-43 single cylinder tests in which anengine is operated under controlled conditions and the amount of sludgeand varnish accumulated on various engine components is visually ratedperiodically on a scale from 0-10 being perfectly clean). The testcriteria is the number of hours until the average sludge and varnishrating drops to 9. The test oil contained 0.08 percent zinc as acommercial zinc dialkyldithiophosphate. The results obtained were asfollows:

A commerical high molecular weight alkenyl succinimide ofpolyethylenepolyamine, e.g., tetraethylenepentamme.

The additives of this invention are useful dispersants in both mineraland synthetic lubricating oils. Examples of mineral lubricating oilsinclude those refined from any crude oil such as Pennsylvania,midcontinent, Gulfcoast, California, and the like. The syntheticlubricants include both the hydrocarbon type and the other various typesof synthetic lubricants. Hydrocarbon synthetic lubricants are generallypolyolefin oligomers or alkylated aromatics. Examples are polybuteneoligomers, styrene isobutylene copolymers, u-decene trimers, tetramers,pentamers, and mixtures thereof, mixtures of alkylated benzenes fromC1246 olefins and having an average molecular weight of 450, and thelike. The polyolefin oligomers are readily prepared from the appropriateolefin by standard oligomerization catalysts such as aluminum chloride,boron trifiuoride, diethyl aluminum chloride, ethyl aluminumsesquichloride, combinations of aluminum alkyls and metal salts such asdiethyl aluminum chloride-titanium tetrachloride, ethyl aluminumsesquichloride-butyl vanadates, triethyl aluminum-zirconium iodides, andthe like.

The alkylated aromatics are made by alkylating aromatics such asbenzene, toluene, naphthalenes, and the like, with olefin mixturespreferably containing C1242 olefins. Catalysts such as AlCl and BF areeffective and the average molecular Weight of the product should be fromabout 300 to 600.

The additives are very effective in synthetic ester type lubricantsincluding monoesters, diesters, complex esters, and the like. Someexamples are C aliphatic monocarboxylic acid esters oftrimethylolpropane, n-hexanoic ester of pentaerythritol, C aliphaticmonocarboxylic esters of equal mole mixtures of trimethylolpropane andpentaerythritol, adipic acid diesters of C monohydric alkanols, complexesters formed by esterifying mixtures of polyols, dicarboxylic acids andmonocarboxylic acids. For example, a useful complex ester is formed bycondensing adipic acid, ethyleneglycol and a C mixture of aliphaticmonocarboxylic acids. Another complex ester is formed fromtrimethylolpropane, adipic acid and C1042 fatty alcohol mixtures. Inessence, the complex esters are condensation products of polycarboxylicacids, polyols, and either monocarboxylic acids or monohydric alkanols,or both.

Other synthetic lubricants include the polyalkyl siloxanes, polyalkylsilicates, alkyl silicones, polyfluoro hydrocarbons, polyaryl ethers,polyalkoxy aryls, polyglycols, and the like.

The lubricant compositions are prepared by merely blending a dispersantamount of the additive With the oil. An effective amount is usually fromabout 0.1 to 5 Weight percent, although more or less can be beneficiallyemployed.

The lubricant compositions can include the other ingredients normallyadded to formulated lubricants. For example, mineral oil and synthetichydrocarbon oil lubricants generally include zincdialkyldithiophosphates, calcium alkyl sulfonates, overbased calciumsulfonates containing colloidal calcium carbonate, calcium phenates,antioxidants such as 4,4'-methylenebis-(2,6-di-tert-butylphenol),2,6-di-tert-butyl-u-dimethyl amino p cresol, phenylene diamines, bariumphosphonates, polyalkyl methacrylate V.I. improvers, and the like.Synthetic ester formulations may include phosphate ester wear inhibitorssuch as tricresyl phosphate, phenyl dicresyl phosphate, and the like,antioxidants such as phenyl-B-naphthyl amine, phenylene diamines,phenothiazines, and the like, metal deactivators, silicone antifoamagents, and the like.

The following examples illustrate the preparation of some preferredlubricant compositions of this invention.

EXAMPLE 17 In a blending vessel is placed 10,000 parts ofsolventrefined, midcontinent, neutral mineral oil SUS). To this is added100 parts of zinc diisobutyl dithiophosphate, parts of overbased calciumalkaryl sulfonate (300 base number), 200 parts of polylaurylmethacrylateV.I. improver, and 50 parts of4,4-methylenebis-(2,6-ditert-butylphenol). Following this, 35 parts ofpolyisobutene pyridinium chloride of Example 3 is added. The mixture iswarmed to 50 C. and stirred until homogeneous, giving a lubricant ofgood stability and excellent dispersant properties suitable for use inautomotive engines.

EXAMPLE 18 In a blending vessel is placed 10,000 parts of a hinderedester lubricant made by esterifying trimethylolpropane with a mixture ofC and C n-aliphatic carboxylic acids. Following this, there is added 100parts of phenyl-anaphthyl amine, 100 parts of dioctyldiphenyl amine, 10parts of l-salicylalaminoguanadine, 300 parts of tricresyl phosphate,and .05 part of dimethyl silicone. Then, 300 parts of the polypropenyltrimethyl ammonium bromide of Example 8 is added. The mixture is warmedto 50 C. and stirred for 15 minutes. It is then filtered to give asynthetic ester lubricant suitable for use in turbines and turbojetengines.

The manner in which the additive is blended with the other lubricantsmentioned is apparent from the foregoing examples.

The additives of this invention are also useful as detergents in liquidhydrocarbon fuels including distillate fuels, such as diesel fuel andliquid hydrocarbon fuels of the gasoline boiling range. Liquidhydrocarbon fuels of the gasoline boiling range are mixtures ofhydrocarbons having a boiling range of from about 80 F. to about 430 F.(ASTM D-86). Of course, these mixtures can contain individualconstituents boiling above or below these figures. These hydrocarbonmixtures contain aromatic hydrocarbons, saturated hydrocarbons andolefinic hydrocarbons. The bulk of the hydrocarbon mixture is obtainedby refining crude petroleum by either straight distillation or throughthe use of one of the many known refining processes, such as thermalcracking, catalytic cracking, catalytic hydroforming, catalyticreforming, and the like. Generally, the final gasoline is a blend ofstocks obtained from several refinery processes. The final blend may'also contain hydrocarbons made by other procedures such as alkylate madeby the reaction of C olefins and butanes using an acid catalyst, such assulfuric acid or hydrofluoric acid.

Preferred gasolines are those having a Research Octane Number of atleast 85. A more preferred Research Octane Number is 90 or greater. Itis also preferred to blend the gasoline such that it has a content ofaromatic hydrocarbons ranging from 10 to about 60 volume percent, anolefinic hydrocarbon content ranging from to about 30 volume percent,and a saturate hydrocarbon content ranging from about 40 to 80 volumepercent, based on the whole gasoline.

The amount of the detergent added to the fuel should be at leastsufficient to exert some detergent action in the fuel induction system.In other words, it should be a detergent amount. Detergent action isgenerally attained when the fuel contains from about 2000 p.p.m. (partsper million) of the new detergent, and more preferably, when it containsfrom about -1000 p.p.m.

The gasoline may contain any of the other additives normally employed togive fuels of improved quality, such as tetraalkyllead antiknocksincluding tetramethyllead, tetraethyllead, mixed tetraethyltetramethyllead, and the like. They may also contain antiknock quantities of otheragents such as cyclopentadienyl nickel nitrosyl, methylcyclopentadienylmanganese tricarbonyl and N- methyl aniline, and the like. Antiknockpromoters such as tert-butyl acetate may be included. Halohydrocarbonscavengers such as ethylene dichloride, ethylene dibromide and dibromobutane may be added. Phosphoruscontaining additives such as tricresylphosphate, methyl diphenyl phosphate, diphenyl methyl phosphate,trimethyl phosphate, and tris(,B-chloropropyl)phosphate may be present.Antioxidants such as 2,6-di-tert-butylphenol,2,6-di-tert-butyl-p-cresol, phenylenediamines such asN-isopropylphenylenediamine, and the like, may be present. Likewise, thegasoline can contain dyes, metal deactivators, or any of the additivesrecognized to serve some useful purpose in improving the gasolinequality.

A preferred embodiment of the invention is a liquid hydrocarbon fuel ofthe gasoline boiling range containing a detergent amount of the newdetergent of this invention and from about 0.25 to 4 grams per gallon oflead as tetraethyllead or tetramethyllead. A still further embodiment ofthe invention is a liquid hydrocarbon fuel of the gasoline boiling rangecontaining a detergent amount of the new detergent of this invention andfrom about 0.005 to 3, more preferably 0.005 to 0.5, grams of manganeseper gallon as methylcyclopentadienyl manganese tricarbonyl.

A highly preferred embodiment of this invention is a liquid hydrocarbonfuel of the gasoline boiling range as previously described containing inaddition to the detergent additive a small amount of a mineral oil. Thisembodiment is particularly advantageous in promoting the cleaning ofintake valves and stems in spark ignited internal combustion engines.The amount of oil added can be any amount from about 0.05 to about 0.5volume percent, based on the final gasoline. Although the oil adjuvantcan be any of the well-known mineral oils including those obtained fromPennsylvania, midcontinent, Gulfcoast, or California crudes, the morepreferred are the naphthenic mineral oils. The viscosity of the mineraloil can vary from about to 2000 SUS at 100 F.

In another preferred embodiment a synthetic olefin oligomer is used inplace of or together with the mineral oil adjuvant. These oligomers areprepared by the polymerization of one or more aliphatic monoolefinichydrocarbons containing from 2 up to about 32 carbon atoms, such asethylene, propylene, butene, decene-l, eicosene-l, tri'acontene-l, andthe like. These result in such adjuvants as polyethylene, polypropylene,ethylene-propylene copolymer, polybutene, styrene-butadiene copolymer,ocdecene trimer, a-decene tetramer and mixtures of the proper averagemolecular weight. Useful polymerization catalysts include both the Lewisacid type such as aluminum chloride, boron trifiuoride, etc., as well asthe metal alkyl types such as triethyl aluminum, diethyl aluminumchloride, methyl aluminum sesquichloride, diethyl zinc, either alone orin combination with a metal salt modifier such as titanium tetrachlorideor cobalt iodide. Means of carrying out the polymerization of the simpleolefin monomers are well known.

The polymerization should be carried out until the olefin forms anormally liquid oligomer having an average molecular weight of fromabout 300 to 2000, especially 350-1500. The oligomers of this molecularweight range have the greatest effect in promoting the cleaning ofintake valves when used in combination with a detergent of thisinvention.

In an especially preferred embodiment the polyolefin adjuvant is anormally liquid olefinic hydrocarbon having an average molecular weightof from about 350 to about 1500 and is made by the polymerization of amixture of aliphatic monoolefins containing at least 12 carbon atoms.Preferably the monoolefins used to prepare this polyolefin adjuvantcontain from about 12-32 carbon atoms and are predominantlyalpha-olefins. These are the polyolefins that are also used in oneembodiment of making the previously-described high molecular quaternaryammonium salts by halogenation and reaction with a tertiary amine. Morepreferred olefin hydrocarbons are those obtained by polymerizing amixture of even numbered, predominantly alpha-monoolefins having from 12to about 32 carbon atoms using a Friedel-Crafts catalyst. PreferredFriedel-Crafts catalysts are aluminum chloride, aluminum bromide, andboron trifluoride. Preferred reaction temperatures are 20 C.120 C. Amost preferred polymerization process is carried out at temperaturesranging from about 40 C. to about C., using an aluminum halide catalystin the absence of any lower alkyl (C -C monohalide.

These poly-C L olefin adjuvants are non-aromatic, normally liquid olefinhydrocarbons characterized by having an average molecular weight rangingfrom 350 to about 1500. By normally liquid" is meant that the olefinhydrocarbon is fluid at room temperature. These olefin hydrocarbonsinclude cyclic olefin hydrocarbons as well as branched-chain andstraight-chain olefin hydrocarbons.

Compositions of typical preferred monoolefin mixtures useful forFriedel-Crafts polymerization are listed in the following table. Thesepreferred monoolefins will be designated herein as C monoolefins or Cmonoolefin mixtures.

Cm MONOOLEFIN MIXTURES [Percent by weight A B O C 4 Olefin carbonnumber:

Total paraifins 18.30 28 18.42 21.87 Other by-prorinntq 2 11, 49 Okeifinconfiguration, percent distribu- 69.7 60.6 60.1 Internal 30.3 39.3 39. 9

1 Vapor phase chromatographic analysis.

9 Estimated.

8 Nuclear magnetic resonance analysis.

4 For this mixture, VPC analysis was based on 91.11% recoverednormalized. The mixture also contained by-product alcohols.

A typical mixture of (2 monoolefins has the following generalcomposition by weight: Cg-Cw olefins-3%, C -C olefins39.2%, 0olefins33.6%, C C parafiins--2%, C -C paraflins19.4%, C paraflins- 0.8%,alcohols-2%.

The following examples will illustrate the preparation of preferrednormally liquid olefin hydrocarbons having a molecular weight of from350 to 1500 by Friedel-Crafts polymerization of mixtures ofu-monoolefins of the type disclosed above. All parts are by weightunless otherwise indicated. The molecular weight of the olefinhydrocarbon products was determined by vapor phase osmometry.

EXAMPLE 19 A vessel was flushed with nitrogen and then charged with 454parts of a C monoolefin mixture. The olefin mixture was cooled to C.; 15parts of aluminum chloride were added to this olefin mixture over a 3-4minute period. The reaction mixture was then heated with stirring at 70C. for 2 hours. The catalyst was then quenched by adding about 150 partsof a 10% HCl solution to the mixture. About 350 parts of hexane wereadded (to facilitate handling) and the diluted mixture was washed withwater until the washings were acid free. The reaction mixture was thenfiltered through Celite. The filtrate was stripped of water and solventunder vacuum on a steam bath. The product obtained was 308 parts of aclear, yellow, very fluid liquid. The molecular weight of this productwas 368.

An analogous product is obtained when the reaction of Example 19 iscarried out at 0 C. for 16 hours; at 145 C. for 30 minutes; or at 40 C.for 5 hours. Boron trifluoride is used with equal effectiveness in placeof aluminum chloride in Example 19.

The gasoline detergent additives of this invention can be added directlyto gasoline or they can be added in the form of a concentrate. Thus,another embodiment of the invention is a gasoline detergent concentratecontaining an additive amount of a detergent of this invention and adiluent. The amount of detergent in the concentrate can vary from about10-90 weight percent. A preferred concentration is from about 35-75weight percent. The diluent serves to maintain the concentrate in aliquid form, making it easy to handle and to meter into gasolineblending systems. Preferred diluents are hydrocarbons including bothaliphatic and aromatic hydrocarbons such as hexane, heptane, octane,petroleum ether, kerosene, benzene, toluene, xylene, and the like,including mixtures thereof. A

more preferred diluent is a higher boiling hydrocarbon such as a mineraloil or polyolefin oligomer. The advantage of using these higher boilinghydrocarbon diluents is that these higher boiling hydrocarbons alsoserve as the previously-described mineral oil or polyolefin adjuvants.Thus, a preferred concentrate contains from about 1090 Weight percent,preferably 3575 weight percent, of the detergent in a mineral oil orpolyolefin oligomer. When this concentrate is added to gasoline a fuelis provided which will maintain the entire induction system in a highdegree of cleanliness.

Especially good results have been obtained when the hydrocarbon diluentemployed in the concentrate is one of the previously-describedpolyolefin oligomers made by polymerizing an olefin or mixture ofolefinic hydrocarbons containing about 12 or more carbon atoms,preferably from 12-32 carbon atoms, to produce a liquid olefin polymerhaving an average molecular weight of about 300-1500.

The detergent concentrate can contain other additives normally used withgasoline, forming an additive package. For example, the concentrate cancontain gasoline antioxidants such as 2,6-di-tert-butylphenol, mixturesof butylated phenol containing about 75 percent of2,6-ditert-butylphenol, 15 percent o-tert-butylphenol,N-isopropylphenylenediamine; phosphorus additives such as tricresylphosphate, trimethylphosphate, phenyldimethylphosphate,dimethylphenylphosphate, tri(/3-chloropropyl) phosphate, and the like;antiknock promoters such as tert-butyl acetate; de-icers such asmethanol, isopropanol, n-butanol, isobutanol; tetraalkyllead antiknockssuch as tetraethyllead, tetramethyllead, redistributedtetraethyltetramethyllead, and the like; scavengers such as ethylenedichloride, ethylene dibromide, dibromobutanes, and the like; otherantiknock agents such as methyl cyclopentadienyl manganese tricarbonyl,ferrocene, methyl ferrocene, cyclopentadienyl nickel nitrosyl,N-rnethylaniline, and the like; metal deactivators such asN,N-disalicylidene-1,2- diaminopropane, dyes; corrosion inhibitors, andthe like.

The concentrates of this invention are readily prepared by merelyblending the ingredients until a homogenous solution is obtained. Thefollowing examples illustrate the preparation of some typicalconcentrates.

EXAMPLE 20 To a blending vessel is added 1000 parts of the detergentproduct from Example 3 and 1000 parts of a naphthenic mineral oil. Themixture is warmed and stirred until homogenous, forming an additiveconcentrate useful for improving the detergent properties of gasoline.

EXAMPLE 21 To a blending vessel is added 1000 parts of the detergentadditive from Example 5 and 1500 parts of the olefin oligomer fromExample 19. Then, 20 parts of a mixture of butylated phenols containingabout 75 percent 2,6-di-tert-butylphenol are added. This mixture isstirred, forming a detergent package which also imparts anti oxidantprotection when added to gasoline.

The amounts of each ingredient in the foregoing compositions can bevaried within wide limits to provide the optimum degree of eachproperty.

Gasoline compositions of this invention can be prepared by merely addingthe detergent in the proper amount to the gasoline base stock andstirring until dissolved. Likewise, the detergent can be injected intothe gasoline stream in an in-line blending system either alone or incombination with other additives such as tetraalkyllead antiknocks.Similarly, the additive concentrate can be added to gasoline, furnishingnot only the detergent but also the adjuvant (mineral oil or olefinoligomer). If desired, the detergent and adjuvant can be separatelyadded to the base gasoline.

The following examples serve to illustrate the manner in which gasolinecompositions of this invention are made.

In these examples the gasoline base stocks have the followingcomposition and properties.

Boiling range F.)

Composition, percent Initial End point Aromatics Olefins saturates 91390 40 1.5 58.5 100 400 35 2 63 95 410 36.5 2.5 61 so 395 49.5 2.5 48105 415 54 1.5 44.5 96 389 39 3 5s 87 395 51 0.5 48.5

EXAMPLE 22 4. A lubricating oil composition of claim 3 wherein In ablending vessel is placed 10,000 gallons of Gasoline H, 25 pounds of thedetergent of Example 3, 100 pounds of the poly-(3 olefin of Example 19,96.5 pounds of tetraethyllead as a commercial antiknock fiuid containingone theory of ethylene dichloride and 0.5 theory of ethylene dibromide,and 15.5 pounds of tricresylphosphate. The mixture is stirred untilthoroughly mixed. The resultant gasoline is a premium grade gasolinewith good detergent properties.

EXAMPLE 23 In a blending vessel is placed 10,000 gallons of Gasoline L,2.5 pounds of detergent of Example 5, and 50 pounds of a neutral mineraloil (viscosity 100 SUS at 100 F.). The mixture is stirred, resulting inan unleaded gasoline having good detergent properties.

EXAMPLES 24-33 The above Examples 22 and 23 are repeated using each ofGasolines I, J, K, M and N.

EXAMPLE 34 To a blending vessel is added 10,000 gallons of Gasoline I,100 pounds of the additive package of Example 17, 84 pounds oftetraethyllead as a commercial antiknock fluid, and 4.8 pounds oftrimethylphosphate. The mixture is stirred, giving a high qualitygasoline of good detergent properties.

Tests were carried out to demonstrate the carburetor detergentproperties of the present additive. In these, the additive was added togasoline which was used to operate a six cylinder L-head engine for 2hours using exhaust recycle to the carburetor. The carburetor is cleanat the start of the test and the criteria of eifectiveness is thecarburetor deposit weight formed. The results obtained were as follows:

1 Average value. 1 Parts per million.

As the test results show, the additives of this invention reducecarburetor deposits to about one-half that normally obtained.

What is claimed is:

1. A lubricating oil containing a dispersant amount of a high molecularweight quaternary ammonium salt having at least one aliphatichydrocarbon group having an average molecular weight of from about3503000 bonded to a quaternary ammonium nitrogen atom, the remaininggroups bonded to said quaternary ammonium nitrogen atom being selectedfrom the group consisting of C alkyl, C hydroxyalkyl, C alkenyl, cyclicgroups which form a morpholine, piperidine or pyridine ring with saidnitrogen atom, and divalent C hydrocarbon groups bridging said nitrogenatom to a second nitrogen atom.

2. A lubricating oil composition of claim 1 wherein said oil is amineral lubricating oil.

said quaternary ammonium halide is a quaternary ammonium chloride.

5. A lubricating oil composition of claim 1 wherein said hydrocarbylgroup bonded to the quaternary ammonium nitrogen atom is a poly-C olefingroup.

6. A lubricating oil composition of claim 5 wherein said poly-C olefingroup is a polypropylene group.

7. A lubricating oil composition of claim 5 wherein said poly-C olefingroup is a polybutene group.

8. A lubricating oil composition of claim 7 wherein said polybutenequaternary ammonium salt is a polybutene pyridinium chloride.

9. A lubricating oil composition of claim 7 wherein said polybutenequaternary ammonium salt is a polybutene tri-C alkyl ammonium chloride.

10. A lubricating oil composition of claim 9 wherein said polybutenetri-lower alkyl ammonium chloride is a polybutene trimethylammoniumchloride.

11. A lubricating oil composition of claim 1 wherein said quaternaryammonium salt is a monoor di-quaternary ammonium salt oftriethylenediamine.

12. A lubricating oil composition of claim 11 wherein said lubricatingoil is a mineral lubricating oil.

13. A lubricating oil composition of claim 12 wherein said aliphatichydrocarbon group bonded to said quaternary ammonium nitrogen atom oftriethylenediamine is a poly-C olefin group.

14. A lubricating oil composition of claim 13, wherein said poly-Colefin group is a polybutene group.

15. A lubricating oil composition of claim 14 wherein said salt is ahalide.

16. A lubricating oil composition of claim 15 wherein said halide ischloride.

17. A lubricating oil composition of claim 5 wherein said poly-C olefingroup has an average molecular weight of about 800-1400.

18. A lubricating oil composition of claim 17 wherein said quaternaryammonium salt is a polybutene tri- C alkyl quaternary ammonium chloride.

19. A lubricating oil composition of claim 18 wherein said quaternaryammonium salt is a polybutene trimethylammonium chloride.

20. A lubricating oil composition of claim 17 wherein said quaternaryammonium salt is a monoor di-quaternary ammonium salt oftriethylenediamine.

21. A lubricating oil composition of claim 20 wherein said salt is achloride.

22. A liquid hydrocarbon fuel of the gasoline boiling range containing adetergent amount of a high molecular weight quaternary ammonium salthaving at least one aliphatic hydrocarbon group having an averagemolecular weight of from about 350-3000 bonded to a quaternary ammoniumnitrogen atom, the remaining groups bonded to said quaternary ammoniumnitrogen atom being selected from the group consisting of C alkyl, Chydroxyalkyl, C alkenyl, cyclic groups which form a morpholine,piperidine or pyridine ring with said nitrogen atom, and divalent Chydrocarbon groups bridging said nitrogen atom to a second nitrogenatom.

23. A fuel composition of claim 22 wherein said aliphatic hydrocarbongroup is a poly-(3 olefin group.

24. A fuel composition of claim 23 wherein said poly- C olefin group isa polybutene group.

25. A fuel composition of claim 24 wherein said salt is selected frompolybutene quaternary ammonium phos phates, mono-alkyl phosphates, anddialkyl phosphates.

26. A fuel composition of claim 24 wherein said salt is a polybutenequaternary ammonium chloride.

27. A fuel composition of claim 26 wherein said polybutene quaternaryammonium chloride is a monoor dipolybutene quaternary ammonium chlorideof triethylenediamine.

28. A fuel composition of claim 23 wherein said poly- C olefin group hasan average molecular weight of about 800-1400.

29. A fuel composition of claim 28 wherein said quaternary ammonium saltis a polybutene tri-C alkyl quaternary ammonium chloride.

30. A fuel composition of claim 29 wherein said quaternary ammonium saltis a polybutene trimethylammonium chloride.

31. A fuel composition of claim 22 containing about 18 0.05 to 0.5volume percent of a normally liquid poly- C2 32 Olefin.

32. A fuel composition of claim 30 containing about 0.05 to 0.5 volumepercent of a normally liquid poly- C2 32 olefin.

33. A fuel composition of claim 32 wherein said polyolefin is a normallyliquid poly-C olefin.

References Cited UNITED STATES PATENTS 3,574,576 4/1971 Honnen et al.4472 3,486,866 12/1969 Stromberg et a1. 4472 2,746,928 5/1956 Darragh eta1. 260-5676 X 2,911,368 11/1959 Fowler et al. 25234 CARL F. DEES,Primary Examiner US. Cl. X.R. 4472; 252

P0-1050 UNITED sTATEs PATENT CEEICE CERTIFICATE OF CORRECTION patent I5,77 ,57 Dated December 11, 1975 I ve t rgf) Robert E. Maleo It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

' In column 2, in the bottom formulaz 1 that portion of the formulareading:

(R should read R) -E that portion of the formula reading:

Signed nd sealed this 7th day of May. 197R.

(SEAL) Attest:

EDX-"IARD I-I.F LETCILER,JR. C. MARSHALL DANN- Attesting OfficerCommissioner of Patents

